Engineering Charge Polarized Au Sites for Low‐Temperature Acetylene Hydrochlorination <jats:title>Abstract</jats:title> <jats:p> Cationic gold catalyzed acetylene hydrochlorination represents a classical landmark in eliminating global mercury pollution, but their sustainable implementation is hindered by acetylene‐dependence design criteria and high operating temperatures. Herein, a platform of carbon‐supported single‐atoms Au catalysts (Au/BC and Au/NC) with polarized charge characteristics are developed via engineering Au sites with hosted B, N configurations. The negatively charged Au/BC catalyst unlocks the low‐temperature inactivity (413–423K) of the Au/NC catalyst while exhibiting superior catalytic performance in the 433–473K operating temperature range. We confirm that the classical scaling relationships on acetylene can be broken by narrowing the adsorption capacity between acetylene and HCl on Au <jats:sup>δ⁻</jats:sup> sites via facilitating the back‐donation of <jats:italic>d</jats:italic> electrons into the antibonding orbitals of acetylene. Prolonging the durability of Au catalysts is achieved through preceding an additional robust Au <jats:sup>δ⁻</jats:sup> → Au <jats:sup>δ⁺</jats:sup> cycle prior to the classic Au <jats:sup>δ⁺</jats:sup> → Au <jats:sup>0</jats:sup> route. This work opens a promising avenue for low temperature vinyl chloride production. </jats:p> 64 29 Wiley